CN102936848B - Method for modifying polyvinyl alcohol fibers and mass concrete with high crack resistance - Google Patents
Method for modifying polyvinyl alcohol fibers and mass concrete with high crack resistance Download PDFInfo
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Abstract
The invention discloses a method for modifying polyvinyl alcohol fibers to be provided with good dispersibility in mass concrete and the mass concrete with the high crack resistance, and belongs to the technical field of building material applications. The method for improving polyvinyl alcohol fibers includes dredging and tidying the polyvinyl alcohol fibers; immersing the dredged and tidied polyvinyl alcohol fibers in spinning oil which contains hydroxypropyl acrylate; and stretching the polyvinyl alcohol fibers, coating an anti-static liquid containing at least one kind of positive ions, cooling and drying the polyvinyl alcohol fibers and cutting the cooled and dried polyvinyl alcohol fibers after being placed statically for 24 hours. The mass concrete with the high crack resistance uses concrete reinforced materials obtained through the modifying method, and the mixing amount of the polyvinyl alcohol fibers is in range of 0.6kg/m3 to 2.0kg/m3. According to the method for modifying polyvinyl alcohol fibers and the mass concrete with the high crack resistance, surfaces of the polyvinyl alcohol fibers are modified, the dispersibility, the hydrophily and the surface anchoring capability of the polyvinyl alcohol fibers in the mass concrete are enhanced, and accordingly, polypropylene fibers are replaced by the polyvinyl alcohol fibers to serve as reinforced materials for the mass concrete and the high crack resistance of the mass concrete is improved.
Description
Technical field
The invention belongs to construction material applied technical field, be specifically related to a kind of method of modifying of vinal and the mass concrete of high cracking resistance energy.
Background technology
Mass concrete refers to water conservancy project large scale structure concrete, as hydraulic structures such as dam, two dams, road, generally no-reinforcing-bar in this xoncrete structure, and its minimum size dimension is generally greater than 5m, and the maximum coarse aggregate size of use is generally 120mm ~ 150mm.Crack-resistant performance of concrete refers to that the ability in crack appears in concrete self opposing cracking or opposing, the index of weighing crack-resistant performance of concrete mainly contains concrete tensile strength, limit stretch value etc., the present invention mainly characterizes concrete cracking resistance with tensile strength and limit stretch value, be that tensile strength and limit stretch value are larger, crack-resistant performance of concrete is better.
Abroad, from since the end of the seventies, polypropylene fiber concrete has been carried out to a large amount of experimental studies, and be used widely in the engineerings such as military affairs, house, traffic, water conservancy.China starts to introduce application at the mid-80.Achievement in research and engineering experience prove, polypropylene fibre can reduce and prevent that concrete from producing in the contraction fissure of plasticity and initial stage hardening phase, thereby improve the performances such as antiseepage, freeze proof, anti-impact mill.Therefore, polypropylene fibre was once used water conservancy project impact-resisting wear-resisting concrete as reinforcing material widely.
End 2009, China's concrete for hydraulic structure industry almost all adopts polypropylene fibre to improve material (reinforcing material) as concrete cracking resistance, according to incompletely statistics, the polypropylene fibre large usage quantity of annual China concrete for hydraulic structure industry application, surpasses hundreds of tons.But the engineering of making a general survey of its use be mostly middle Small Hydropower Project (it is generally acknowledged that the following engineerings of 100 meters of concrete heights of dam are medium and small project, concrete height of dam be large-scale hydroelectric project at 100 meters ~ 200 meters, 200 meters of heights of dam above be mega-construction project).
End 2009, vinal does not all have must be utilization in concrete for hydraulic structure, traces it to its cause, and is mainly reflected in following two aspects:
1) vinal price is expensive compared with polypropylene fibre--the market factor;
2) main factor is that the self property of vinal determines that it is difficult to disperse in concrete compared with polypropylene fibre, and therefore, vinal cannot apply in mass concrete so far--technical factor.
Along with the further reduction of vinal production cost, the input with country in hydroelectric project strengthens, and simultaneously in conjunction with the further modification to vinal in the present invention, makes vinal become possibility in the utilization of concrete for hydraulic structure.
Of the present inventionly to the effect that vinal is applied to hydraulic large-volume concrete, make it improve the cracking resistance of mass concrete.Make a general survey of in current concrete technology, only have the application technology of polypropylene fibre in concrete for hydraulic structure, similar to content of the present invention, the polypropylene fibre of therefore usining carries out comparative illustration at the application technology of concrete for hydraulic structure as prior art.
Mainly there is following shortcoming in the technology that adopts polypropylene fibre to apply to concrete for hydraulic structure at present:
1) because of its elastic modelling quantity and tensile strength, limited (elastic modelling quantity is 3.5 ~ 5GPa to polypropylene fibre, tensile strength is 450 ~ 600MPa), can only play the effect of raising to concrete early stage (it is generally acknowledged after concrete formation within 7d) tensile strength and limit stretch value, and can not play raising effect to the middle and later periods limit stretch value of mass concrete;
2) test is found, the polypropylene fibre raising early stage tensile strength of mass concrete and the amplitude of limit stretch value are less, is difficult to impel the cracking role of concrete opposing self, and therefore, more polypropylene fiber concrete also exists more cracking phenomena.
For overcoming the above problems, the present invention solves above problem by changing better reinforcing material.
Summary of the invention
Technical problem to be solved by this invention is to provide a kind of method of modifying that makes vinal have good dispersion in mass concrete, and a kind of mass concrete with high cracking resistance energy is provided.
The technical solution adopted for the present invention to solve the technical problems is:
The method of modifying of vinal, combs logical arrangement with combing device to the vinal that on production line, spun wait stretches; To immerse in spinning oil through the logical vinal long filament arranging of comb, described spinning oil contains hydroxypropyl acrylate; By dip-coating the filament draw of spinning oil, then coating at least contain a kind of cationic antistatic liquid, cooling drying, becomes the coil of wire by winding filament afterwards; The static placement of the coil of wire cut off for 24 hours above, obtains having the short vinal of good dispersion in concrete.
Wherein, the mixed liquor that described in said method, spinning oil is comprised of the vinyltriethoxysilane of the hydroxypropyl acrylate of 13～17 weight portions, the dimethylaminoethyl acrylate methyl ammonia ethyl ester of 5～7 weight portions and 3～5 weight portions carries out emulsion polymerisation and makes under the effect of ammonium persulfate.
Further, the mixed liquor that described spinning oil is comprised of the vinyltriethoxysilane of the hydroxypropyl acrylate of 15 weight portions, the dimethylaminoethyl acrylate methyl ammonia ethyl ester of 6 weight portions and 4 weight portions carries out emulsion polymerisation and makes under the effect of ammonium persulfate.
Wherein, described in said method, antistatic liquid is by the palmitate quaternary ammonium salt of 40～50 weight portions, the mixing of the phosphate polyethylene glycol of the dimethyl suflfate of 30～36 weight portions, 20～24 weight portions makes.
Further, described antistatic liquid is by the palmitate quaternary ammonium salt of 45 weight portions, the mixing of the phosphate polyethylene glycol of the dimethyl suflfate of 33 weight portions, 22 weight portions makes.
Further, the molecular weight of described phosphate polyethylene glycol is between 1000～4000.
Modified polyvinyl alcohol fabric, is made by the method for modifying described in above-mentioned any one.
The mass concrete of high cracking resistance energy, with above-mentioned modified polyvinyl alcohol fabric, as concrete reinforcing material, the volume of vinal is 0.6～2.0kg/m
3.
Wherein, the volume of vinal is 0.9～1.5kg/m
3.
The invention has the beneficial effects as follows: the present invention by spun vinal being dredged to arrangement, immerse spinning oil, stretching, the coating contain hydroxypropyl acrylate and contain cationic antistatic liquid, be coiled into the processing such as the static placement of the coil of wire, polyvinyl alcohol is carried out to surface modification, strengthen its dispersiveness, hydrophily and surface anchoring ability in mass concrete, thereby substitute polypropylene fibre as the reinforcing material of mass concrete, improve the cracking resistance of mass concrete.
The specific embodiment
Below by the specific embodiment, the present invention is further described.
The method of modifying of vinal, combs logical arrangement with combing device to the vinal that on production line, spun wait stretches; To immerse in spinning oil through the logical vinal long filament arranging of comb, described spinning oil contains hydroxypropyl acrylate; By dip-coating the filament draw of spinning oil, then coating at least contain a kind of cationic antistatic liquid, cooling drying, becomes the coil of wire by winding filament afterwards; The static placement of the coil of wire cut off for 24 hours above, obtains having the short vinal of good dispersion in concrete.
Preferably, for further dispersiveness, hydrophily and the surface anchoring ability of enhanced polyethylene alcohol fiber, the mixed liquor that spinning oil described in said method is comprised of the vinyltriethoxysilane of the hydroxypropyl acrylate of 13～17 weight portions, the dimethylaminoethyl acrylate methyl ammonia ethyl ester of 5～7 weight portions and 3～5 weight portions carries out emulsion polymerisation and makes under the effect of ammonium persulfate.
Further, the mixed liquor that described spinning oil is comprised of the vinyltriethoxysilane of the hydroxypropyl acrylate of 15 weight portions, the dimethylaminoethyl acrylate methyl ammonia ethyl ester of 6 weight portions and 4 weight portions carries out emulsion polymerisation and makes under the effect of ammonium persulfate.
Preferably, for dispersiveness, hydrophily and the surface anchoring ability of further enhanced polyethylene alcohol fiber, the liquid of antistatic described in said method is by the palmitate quaternary ammonium salt of 40～50 weight portions, the phosphate polyethylene glycol of the dimethyl suflfate of 30～36 weight portions, 20～24 weight portions mixes makes.
Further, described antistatic liquid is by the palmitate quaternary ammonium salt of 45 weight portions, the mixing of the phosphate polyethylene glycol of the dimethyl suflfate of 33 weight portions, 22 weight portions makes.
Further, the molecular weight of described phosphate polyethylene glycol is between 1000～4000.
Modified polyvinyl alcohol fabric, is made by above-mentioned method of modifying.
The mass concrete of high cracking resistance energy, with above-mentioned modified polyvinyl alcohol fabric, as concrete reinforcing material, the volume of vinal is 0.6～2.0kg/m
3.
Preferably, the volume of vinal is 0.9～1.5kg/m
3.
Below by embodiment, the specific embodiment of the invention is further described, but therefore protection scope of the present invention is not limited among embodiment.
The modification of embodiment mono-vinal and the performance after modification
With combing device, the vinal that on production line, spun wait stretches is combed to logical arrangement; To immerse in spinning oil through the logical vinal long filament arranging of comb, described spinning oil contains hydroxypropyl acrylate; By dip-coating the filament draw of spinning oil, then coating at least contain a kind of cationic antistatic liquid, cooling drying, becomes the coil of wire by winding filament afterwards; The static placement of the coil of wire cut off for 24 hours above, obtains having the short vinal of good dispersion in concrete.The mixed liquor that described spinning oil is comprised of the commercially available vinyltriethoxysilane of the commercially available hydroxypropyl acrylate of 15 weight portions, the commercially available dimethylaminoethyl acrylate methyl ammonia ethyl ester of 6 weight portions and 4 weight portions carries out emulsion polymerisation and makes under the effect of ammonium persulfate; Described antistatic liquid is by the commercially available palmitate quaternary ammonium salt of 45 weight portions, the commercially available phosphate polyethylene glycol of the commercial sulfuric acid dimethyl ester of 33 weight portions, 22 weight portions mixes makes, and the molecular weight of described phosphate polyethylene glycol is between 1000～4000.
1, the difference of the technical indicator of polypropylene fibre and modified polyvinyl alcohol fabric, as shown in table 1:
Table 1 PP fiber and modified PVA fiber main performance index of the present invention
As can be seen from Table 1, modified polyvinyl alcohol fabric density of the present invention is greater than 1, and compared with water weight, and polypropylene fibre is light compared with water; Vinal tensile strength and elastic modelling quantity are far above polypropylene fibre.Above index is all conducive to vinal and better in concrete, disperses, and is conducive to the toughening effect that it brings into play self in maturing.The elastic modelling quantity of PVA fiber exceeds 1 magnitude compared with the elastic modelling quantity of PP fiber, this makes PVA fiber when the stressed fracture of concrete, can absorb very large energy, also be that PVA fiber concrete also can bear the more failing load of macro-energy, thereby strengthened concrete toughness, improved the cracking resistance of mass concrete.Though and the fracture elongation of polypropylene fibre is high, do not need so large percentage elongation in concrete.
2, surface roughness: the rough surface of modified PVA fiber of the present invention, is different from other fibers such as polypropylene fibre, the physics anchor force between energy fortifying fibre and cement material, the cracking resistance of raising mass concrete.
3, PVA fiber is different from the chemical composition of PP fiber, hydroxyl in PVA fiber can be effectively combined with water, cement-based material, form hydrogen bond, PVA fiber is hydrophilic fibre, and PP fiber is hydrophobic fiber, the present invention is by the modification to PVA fiber, strengthen its hydrophily, make space unharmful to concrete antifreezing between PVA fiber surface and cement-based material, the also effective interfacial adhesion of fortifying fibre and cement-based material simultaneously, the cracking resistance that improves mass concrete, this is that polypropylene fibre cannot possess.
Embodiment bis-mass concrete of the present invention
The present invention has carried out concrete performance test research to following several situations:
Sequence number 1: the dam concrete (as benchmark) of not mixing fiber;
Sequence number 2: the dam concrete (keeping consistent with the dam concrete gel material content of not mixing fiber) of mixing the modified PVA fiber of 0.4kg/m3;
Sequence number 3: the dam concrete (keeping consistent with the dam concrete gel material content of not mixing fiber) of mixing the modified PVA fiber of 0.6kg/m3;
Sequence number 4: the dam concrete (keeping consistent with the dam concrete gel material content of not mixing fiber) of mixing the modified PVA fiber of 0.9kg/m3;
Sequence number 5: the dam concrete (keeping consistent with the dam concrete gel material content of not mixing fiber) of mixing the modified PVA fiber of 1.2kg/m3;
Sequence number 6: the dam concrete (keeping consistent with the dam concrete gel material content of not mixing fiber) of mixing the modified PVA fiber of 1.5kg/m3;
Sequence number 7: the dam concrete (keeping consistent with the dam concrete gel material content of not mixing fiber) of mixing the modified PVA fiber of 2.0kg/m3;
Sequence number 8: the dam concrete (keeping consistent with the dam concrete gel material content of not mixing fiber) of mixing the PP fiber of 0.9kg/m3;
Sequence number 9: the dam concrete (keeping consistent with the dam concrete gel material content of not mixing fiber) of mixing the unmodified PVA fiber of 0.9kg/m3.
Respectively above 9 kinds of situations are carried out to the tests such as mixing concrete performance, mechanical property, deformation performance, endurance quality, cracking resistance.
1, mix and stir performance
Test is by match ratio parameter and mix and stir performance test results, as shown in table 2
The mix performance test results of table 2 different situations
As can be seen from Table 1: in the situation that Binder Materials is identical, on the basis of dam concrete of not mixing fiber, mix the modified PVA fiber of unmodified PVA fiber, PP fiber, different addition quantity outward, by adjusting water reducer and air entraining agent volume, substantially kept concrete slump and air content within less distribution.
2, mechanics and deformation performance
Result of the test is as shown in table 3.
Table 3 mechanics and deformation performance result of the test
As can be seen from Table 3:
(1) water-cement ratio because of the combination of several situations is identical, gel material content is consistent, so the compression strength of 28d, 90d, elastic modelling quantity differ less;
(2) mix 0.6～2.0kg/m
3the dam concrete of modified PVA fiber, do not mix the normal concrete of fiber, split tensile strength and the axial tensile strength of its 28d, 90d are all improved to some extent, the different increase rates of volume are different;
(3) mix 0.6～2.0kg/m
3the dam concrete of modified PVA fiber, the limit stretch value of its 28d, 90d is not mixed the normal concrete of fiber, has raising by a relatively large margin, wherein mixes 0.9～1.5kg/m
3modified PVA fiber time, increase rate is maximum;
(4) mix 0.9kg/m
3unmodified PVA fiber with mix 0.9kg/m
3pP fiber, all can not make the limit stretch value of dam concrete and tensile strength be significantly improved.
3, cracking resistance
Process of the test is set forth: utilize temperature stress testing machine, the crack resistance in length of time morning of the fiber concrete of variety classes/volume is mixed in research.Four grading concrete mix wet screenings are greater than to the coarse aggregate of 40mm to reject particle diameter, then, in the inner cast of testing machine, adopt vibrating spear to carry out jolt ramming, start to test after floating.After on-test, the synchronous motor startup of testing machine is to guarantee that test specimen is in 100% restrained condition, and testing machine is followed the tracks of test specimen inside center temperature simultaneously, and test specimen is heated up under half thermal insulation/adiabatic condition; When test specimen temperature reaches (being inside center temperature stabilization) after peak value, test specimen is lowered the temperature, rate of temperature fall be 1 ℃/(3～5) minute, until test specimen cracking.
Result of the test is as shown in table 4:
The key parameter that table 4 temperature stress testing machine test obtains
(1), while mixing 0.9kg/m3 modified PVA fiber, concrete Cracking Temperature is-7.3 ℃; While mixing unmodified PVA fiber, concrete Cracking Temperature is-2.0 ℃; While mixing PP fiber, concrete Cracking Temperature is-1.0 ℃.
(2) with Cracking Temperature, evaluate the concrete crack resistance in length of time morning, mix 0.9kg/m
3the crack resistance of modified PVA fiber dam concrete is best.
4, endurance quality
To water conservancy project dam concrete, generally, with freeze proof and impervious index, evaluate its endurance quality, this result of the test to endurance quality is shown in Table 5.
Table 5 endurance quality result of the test
As can be seen from Table 4, mix the modified PVA fiber of 0.9kg/m3, unmodified PVA fiber, PP fiber outward and all can not produce larger side effect to the impervious grade of dam concrete and freeze proof grade.
5, the engineer testing in dam concrete of modified PVA fiber
(1) laboratory's dispersivity test
The engineer testing of the modified PVA fiber arriving involved in the present invention is mainly the feeding sequence test of modified PVA fiber.Whether evaluate the method for this test, be mainly to adopt naked-eye observation modified PVA fiber in mass concrete, to disperse evenly to judge.
Test has adopted following several feeding modes:
1) great Shi+especially big stone → concrete and coal ash → middle stone+gravelstone → sand → water → modified PVA fiber;
2) great Shi+especially big stone → concrete and coal ash → middle stone+gravelstone → modified PVA fiber → sand → water;
3) great Shi+especially big stone → concrete and coal ash → modified PVA fiber → middle stone+gravelstone → water → sand;
4) great Shi+especially big stone → concrete and coal ash → modified PVA fiber → middle stone+gravelstone → sand → water.
Find the 2nd) with the 4th) kind mode is when mix and stir in laboratory, adds first dry mixing 10s～20s before water; Can make modified PVA fiber better disperse in dam concrete, therefore, in the situation that using identical fibre, the operation of mixing and stirring of the best of the present invention is before adding water, to drop into modified PVA fiber, carries out the dry mixing of certain hour simultaneously.
(2) batching plant dispersivity test
Through groping fiber dispersion in laboratory, in construction batching plant, adopt first by modified PVA fiber dry mixing 5s(self-dumping mixer together with coarse aggregate, fine aggregate, Binder Materials), then add water (containing additive) and mix and stir (this step mixing time is determined by specific construction machinery).By batching plant trial mix at the scene, show that modified PVA fiber is better dispersed in dam concrete.
Embodiment in conjunction with test with theoretical to the performance after the modification of vinal of the present invention and modification and mass concrete the performance after using this modified polyvinyl alcohol fabric done concrete description, illustrate to adopt the method for modifying of the present invention can dispersiveness, hydrophily and the surface anchoring ability of enhanced polyethylene alcohol fiber in mass concrete, thereby the vinal that use method of modifying of the present invention makes has better cracking resistance as the mass concrete of reinforcing material.
Claims (7)
1. the method for modifying of vinal, is characterized in that: with combing device, the vinal that on production line, spun wait stretches is combed to logical arrangement; To immerse in spinning oil through the logical vinal long filament arranging of comb; By dip-coating the filament draw of spinning oil, then coating at least contain a kind of cationic antistatic liquid, cooling drying, becomes the coil of wire by winding filament afterwards; The static placement of the coil of wire cut off for 24 hours above, obtains having the short vinal of good dispersion in concrete; Wherein, the mixed liquor that described spinning oil is comprised of the vinyltriethoxysilane of the hydroxypropyl acrylate of 13～17 weight portions, the dimethylaminoethyl acrylate methyl ammonia ethyl ester of 5～7 weight portions and 3～5 weight portions carries out emulsion polymerisation and makes under the effect of ammonium persulfate; Described antistatic liquid is by the palmitate quaternary ammonium salt of 40～50 weight portions, the phosphate polyethylene glycol of the dimethyl suflfate of 30～36 weight portions, 20～24 weight portions mixes makes.
2. the method for modifying of vinal according to claim 1, is characterized in that: the mixed liquor that described spinning oil is comprised of the vinyltriethoxysilane of the hydroxypropyl acrylate of 15 weight portions, the dimethylaminoethyl acrylate methyl ammonia ethyl ester of 6 weight portions and 4 weight portions carries out emulsion polymerisation and makes under the effect of ammonium persulfate.
3. the method for modifying of vinal according to claim 1, is characterized in that: described antistatic liquid is by the palmitate quaternary ammonium salt of 45 weight portions, the phosphate polyethylene glycol of the dimethyl suflfate of 33 weight portions, 22 weight portions mixes makes.
4. the method for modifying of vinal according to claim 1, is characterized in that: the molecular weight of described phosphate polyethylene glycol is between 1000～4000.
5. modified polyvinyl alcohol fabric, is characterized in that: by the method for modifying described in any one in claim 1～4, made.
6. the mass concrete of high cracking resistance energy, is characterized in that: with modified polyvinyl alcohol fabric claimed in claim 5, as concrete reinforcing material, the volume of vinal is 0.6～2.0kg/m
3.
7. the mass concrete of high cracking resistance energy according to claim 6, is characterized in that: the volume of vinal is 0.9～1.5kg/m
3.
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| CN103852384B (en) * | 2014-03-11 | 2016-08-31 | 中交四航工程研究院有限公司 | A kind of concrete capacity against cracking quantizes evaluation methodology |
| CN104562706B (en) * | 2014-12-23 | 2016-07-06 | 江苏苏博特新材料股份有限公司 | A kind of POM fiber with anti-carbonization function |
| CN105887246B (en) * | 2016-04-28 | 2018-03-30 | 常州市灵达化学品有限公司 | A kind of cement products vinal spinning oil |
| CN108867045B (en) * | 2017-05-09 | 2021-02-23 | 中国石油化工股份有限公司 | Graft modified vinylon fiber for fracturing and preparation method thereof |
| CN109403038B (en) * | 2017-08-17 | 2021-11-26 | 中国石油化工股份有限公司 | Cationic polymer surface grafted vinylon fiber and preparation method thereof |
| CN108249798B (en) * | 2018-01-11 | 2021-01-12 | 东南大学 | Modification method of polyvinyl alcohol fiber for high-ductility cement-based composite material |
| CN109516726A (en) * | 2018-11-21 | 2019-03-26 | 中国电建集团成都勘测设计研究院有限公司 | Sealing off and covering anchorage material suitable for flow turbulence area anchor cable |
| CN114075061B (en) * | 2021-10-29 | 2022-08-09 | 广东粤盛特种建材有限公司 | Efficient special fiber anti-cracking agent and preparation method thereof |
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Address after: The North Qingyang District of Chengdu City, Sichuan Province, No. 610072 Applicant after: Chengdu Hydroelectric Investigation & Design Institute of SPC Applicant after: Jiangsu Nengli Technology Co., Ltd. Address before: The North Qingyang District of Chengdu City, Sichuan Province, No. 610072 Applicant before: Chengdu Hydroelectric Investigation & Design Institute of China Hydropower Consu Applicant before: Jiangsu Nengli Technology Co., Ltd. |
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Address after: The North Qingyang District of Chengdu City, Sichuan Province, No. 610072 Applicant after: Co., Ltd of Chengdu survey and design academy of electricity Jian group of China Applicant after: Jiangsu Nengli Technology Co., Ltd. Address before: The North Qingyang District of Chengdu City, Sichuan Province, No. 610072 Applicant before: Chengdu Hydroelectric Investigation & Design Institute of SPC Applicant before: Jiangsu Nengli Technology Co., Ltd. |
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